In this work, the complementary use of Fourier transform infrared (FT-IR) spectroscopy, conventional micro-Raman spectroscopy and UV-Raman scattering proved successful for the characterization of bulk minerals and of a variety of pigments from decorated finishing layers of plasters from a Roman archaeological site known as Villa dei Quintili, a monumental residence located in the south-eastern part of Rome (Italy). The used multi-technique approach provided insights on the pictorial technique, giving information that could be useful for proper restoration. It is worth underlining that the present study represents the first attempt of carrying out UV resonance Raman measurements for analysing cultural heritage materials.